Anti-rust compositions



7 ANTI-RUST COMPOSITIONS Allen E. Brehm, 'Gritfith, Ind., assignor to Standard on Company, Chicago, 11]., a corporation of Indiana I 7 N9 Drawing. Filed Oct. 17,1956, Ser. No. 616,387

Claims. (CI. 44-66) This invention relates to improved corrosion and/ or rust inhibited Oleaginous products, particularly to normally liquid hydrocarbon products inhibited to provide improved 'anti corrosion and/or anti-rust properties.

2,948,598 Patented Aug. 9, .1960

, in the oleaginous compounds, such as hydrocarbon oils,

petroleum Oils, fatty oils, and particularly normally liquid hydrocarbons, such as lubricating oils, turbine oils, kerosome, fuel and heater oils, diesel oils, motor fuels, naphthas, etc., small amounts, .sufficient to inhibit corrosion I and/ or rusting of perfloroalkyl surfaceactive agentcoin- "The rusting of steel used in the transportation and stor- H age of'petroleum products has always presented a serious problem; The rusting of pipe lines and tanks used to transport petroleum light oil products represents per se a substantial annual economic loss in maintenance and replacement costs. In addition, the presence of sediment and rust as aresult of corrosion and'carry-over into fuel burninginstallations creates fuel quality and operating problems. The situation is particularly acute in the case of aviation gasoline where the hazard of engine stoppage through clogging of filters and carburetion equipment presents special hazards but'applies to the handling and use of motor and diesel fuels as well. The rusting of storage tanks used. to supply industrial and household burner'installations presents serious problems. In addition to the possibility of the storage tank rusting through, there is the danger that filters and fuel lines may become clogged, causing operating failure of the burner.

The problem of corrosion by rusting is associated with the presence of moisture in the oil products by entrainment, r condensation and solution. In most cases, the problem is accentuated by the presence of a separate water phase. Thus, in the storage and bulk shipment of light products such as gasoline, it is common practice to mainpounds of the type hereinafter described and in combination therewith a polymerized carboxylic acid such as dilinoleic acid, trilinoleic acid or mixtures of suchpoly merized acids. The perfluoroalkyl compound and the polymeric high molecular weight unsaturated carboxylic acid are suitably used in concentrations of from about 0.0001% to about 1%, and preferably from about 0.0002% to about 0.5 in ratios of from 1:2 to 2:1 respectively, but preferably 1:1.

The polymeric high molecular weight unsaturated carboxylic acids have molecular weights above about 300. While essentially pure polymeric acids such as dimerized linoleic acid, having a molecular weight of about 600 can be used, it is preferable, because of their availability, to use commercial polymerized high molecular Weight unsaturated carboxylic acids.

A useful, commercially available dimeric carboxylic acid is commercially available from Emery Industries lnci under the trade name Emery 95 S-Dimer Acid. Since the commercial product is produced by dimerization of tain a water layer as tank bottoms. Even where a. water 2'.

layer is not used as tank bottoms, a separate Water phase may form by repeated condensation of moisture, associated with tank breathing or the alternate expansion and contraction of the bulk with temperature changes, unless special precautions aretaken. The problem of complete possess anti-rust properties. Among the most, eifective 3.

are organic acids, particularly fatty acids and organic acids of phosphorus and sulfur, as well as esters and amine or amide salts thereof. In general, materials of this type provide reasonably successful protection against rusting of. met-al surfaces exposed to an oil phase. Protection against rusting in the water phase, however, for the most part is lacking or is seriously deficient.

It is anobject of this invention to provide a normally liquid oleaginous composition having improved rust and/ or lcorrosioninhibiting properties for the protection of metalsurfaces of oil storage and/ or handling equipment, whether exposed to the oil or to the Water phase. Another object of the invention is to provide a rust inhibiting hydrocarbon oil composition. Still another object of the invention is to provide a normally liquid motor fuel and fuel oil composition which will inhibit the rusting and/or corrosion of metal surfaces of storage and/or handling equipment for such fuel. Further objects and advantages of the invention will become apparent from the following description thereof. I

The foregoing objects can be attained by incorporating linoleic acid, it is usually referred to as 'dilinoleic acid. The commercial acid typically contains about 85% of the dilinoleic acid, about 12% -of trilinoleic acid and about 3% of monomeric acid.

; Typical specifications for the commercial product are as follows:

Iodine value 80-95 Acid value 180-192 Saponification value 185-l95 Unsaponifiable 2.0% max. Color, Gardner 12 max. Neutralization equivalent 290-310 Refractive index at 25 C. 1.4919 Specific gravity at 15.5" C./l5. 5 C. 0.95 Flash point, F. 530 Fire point, F. 600 Viscosity at 25 C. (Gardner-Holdt) Z4 Viscosity at 25 C., centistokes 10,000 Viscosity at 100 C., centistokes 100 The most satisfactory acid for use in forming the new inhibitors, measured in terms of anti-rust effectiveness, is a mixture of polymerized fatty acids predominating in trilinoleic acid. A particularly satisfactory acid is commercially available from the W. C. Hardesty Company under the trade name of D-SO Acid. Another suitable .product is marketed by Rohm & Haas Company under the trade name VR-l Acids. Such acids may be produced as by-product still-residues in the manufacture of 'sebacic acid by the distillation of castor oil in the presence of caustic. A method of obtaining such by-product still? residues in the preparation of sebacic 'acidjisde'scribed in U.S. 2,470,849 issued to W. E. Hanson, May 24,1949} The mixture of high molecularweight unsaturated fatty acids comprises monomers, dimers, trimers and higher polymers in the ratio of fron'11about45 'to'about55 of a monomers and dimers fraction having a molecular Weight in the range of from about 300 to 600, and from about 45% to about 55% of a trimers and higher polymer fraction having a molecular weight in excess of 600. The fatty acid polymers result in part from a thermal polymerization of fatty acid type constituents of the caster oil, and in part from other reactions, such as the inter-molecular esterification, of such acid to form high molecular weight products. The acid mixture, D-SO Acid, supra, which is mainly a mixture of polymeric long chain poly- The perfiuoroalkyl surface active agents particularly well suited for the herein described invention are perfluoroalkyl amides having the general formula nFM NH n HZn N( ans...)xr n' nzndoya in which n is an integer 6 to 10 inclusive, n is an integer 1 to 3, n" is an integer 1 to 12 inclusive, x.is2 to 3, y is, to 1, Z is chlorine, bromine or iodine and z is 0 to 1. Examples of specific compounds of the above formulation are The effectiveness of the herein described invention in inhibiting rusting in both the oil phase and in the water phase of a system is demonstrated by the data in Table I. These data were obtained in a static rust test in which black iron test specimens /2" x x cleaned with emery cloth and steel wool, are placed in a tall four ounce glass container in which are placed 100 cubic centimeters of the liquid to be tested, and allowed to stand for 30 minutes. Ten cubic centimeters of tap water are then added and the cork container rolled on its side for about one minute, after which it is returned to an upright position. At the end of sixteen hours the test specimens are examined for rusting by visual inspection, and the percent area rusted estimated.

The following samples were subjected to the above test:

Sample l-Gasoline Sample 2-Gasoline+002% 1 polymeric fatty acids 2 Sample 3-Gasoline+002% C7F15CONHC3H6N(CH3)3I Sample 4-Gasoline+002% *Mixture of polymeric fatty acids predominating in trilinoleic acid (Hardesty D-50 Acid).

Table I Percent Rust Percent Rust Test Sample in Gasoline in ater Layer Layer 6. 1, spots- 20.

2 1, 5 spotsnone The above data demonstrate the synergistic effect of the two additives. Although test samples 2 to 5 inclusive show that the polymeric fatty acids and the perfluoroalkyl surface active agents exhibit rust inhibiting properties in the hydrocarbon or oil phase, substantially no or very =litle rust inhibitingin thewater phase is shown. However, the combination of the polymeric fatty acids and the perflworoalkyl surface active agents (test samples are weight percentages unless otherwise stated.

I claim:

1. A composition consisting essentially of a major pro portion of a normally liquid non-lubricating mineral oil fraction, from about 0.000l% to about 1.0% of a polymeric high molecular weight unsaturated carboxylic acid having a molecular weight above about 300 selected from the group consisting of dilinoleic acid and polymerized castor oil fatty acids consisting essentially of from about 45% to about 55% of a monomer and dimer fraction having a molecular weight of from about 300 to about 600 and fromiabout 45% to about 55 of a trimer and higher polymer fractionhaving a molecular Weight in excess of about 600, and from about 0.0001% to about 1.0% of a perfluoroallgyl surface active agent having the general formula C F cONHC lfl 'lvl( C,,'H ),;(C ''H ),,Z in which n is an integer 6 to 10 inclusive, n is an integer 1 to 3, n" is an integer 1 to 12 inclusive, x is an integer 2 to 3, y is an integer 0 to 1, Z is a halogen selected from the group consisting of bromine and iodine, and z is an integer 0 to 1, said polymeric acid and said perfluoroalkyl surface active agent being employed in the ratio of 2:1 to 1:2 respectively.

2. A composition as described in claim 1 in which the perfluoroalkyl surface active agent has the formula C-,F CONHC H N(CH I 3. A composition as described in claim 1 in which the perfluoroalkyl surface active agent has the formula C7F 1 C H Br 4. A composition as described in claim 1 in which the perfluoroalkyl surface active agent has the formula C F CONHC Hs (C a)2 5. A composition as described in claim 1 inrwhich a non-lubricating hydro-carbon oil is a hydrocarbon oil fraction distilling in the gasoline distillation range.

6,. A composition as described in claim 1 in which .a non-lubricating hydrocarbon oil is a fuel oil.

References Cited in the file of this patent UNITED STATES PATENTS 2,632,695 Landis et al. Mar. 24,, 1953 2,680,717 Little June 8, 1954 2,764,603 Ahlbrecht Sept. 25, 1956 2,814,593 Beiswanger et a1. Nov. 26, 19 57 UNITED STATES PATENT OFFICE v CERTIFICATE CI CORRECTION Patent No. 2,948 598 v August 9, .1960

Allenj Brehm Iti's hereby certified that error appears in the printed specification w of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2 line 68 for "caster" read castor column 3 D H line 43, for "002% polymeric fatty acids read 002% polymeric fatty acids line 46 the formula should appear as shown below instead of as in the patent:

C7F CONHC H N(CH3) C OH BI" same column 3, lines 52 53 and 54, the footnotes following Sample 8 should read as shown below instead of as in the patent:

Mixture of polymeric fatty acids predominating in trilinoleic acid (Hardesty "D-5O Acid") 0 0.002% (wQ)=5 lbse additive per 1000' barrels gasolineo Signedand sealed this 18th day of April 1961.,

(SEAL) Attest: I

ERNEST .SWIDER DAVID L. LADD Attest'lng Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,948,598 August 9I 1960 AllenjE'a. Brehm It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2 line 68 for "caster" read Castor column 3 line 43, for "OO2% polymeric fatty acids read 002% polymeric fatty acids line 46, the formula should appear as shown below instead of as in the patent:

C7F CONHC H N(CH3) C H BP same column 3, lines 52 53 and 54l the footnotes following Sample 8 should read as shown below instead of as in the patent:

Mixture of polymeric fatty acids predominating in trilinoleic acid (Hardesty "D-5O Acid") v p 0.002% (w)=5 lbs, additive per 1000. barrels gasoline. 0

Signed and sealed this 18th day of April 1961:,

(SEAL) Attest:

ERNEST .sw'IDER DAVID L. LADD Attest'lng Officer Commissioner of Patents 

1. A COMPOSITION CONSISTING ESSENTIALLY OF A MAJOR PROPORTION OF A NORMALLY LIQUID NON-LUBRICATING MINERAL OIL FRACTION, FROM ABOUT 0.0001% TO ABOUT 1.0% OF A POLYMERIC HIGH MOLECULAR WEIGHT UNSATURATED CARBOXYLIC ACID HAVING A MOLECULAR WEIGHT ABOVE ABOUT 300 SELECTED FROM THE GROUP CONSISTING OF DILINOLEIC ACID AND POLYMERIZED CASTOR OIL FATTY ACIDS CONSISTING ESSENTIALLY OF FROM ABOUT 45% TO ABOUT 55% OF A MONOMER AND DIMER FRACTION HAVING A MOLECULAR WEIGHT OF FROM ABOUT 300 TO ABOUT 600 AND FROM ABOUT 45% TO ABOUT 55% OF A TRIMER AND HIGHER POLYMER FRACTION HAVING A MOLECULAR WEIGHT IN EXCESS OF ABOUT 600, AND FROM ABOUT 0.0001% TO ABOUT 1.0% OF A PERFLUOROALKLY SURFACE ACTIVE AGENT HAVING THE GENERAL FORMULA 